Substituted benzohydroxamates



United States Patent 3,352,899 SUBSTITUTED BENZOHYDROXAMATES KanjiTaniguchi, Fujisawa-shi, Mitsuo Asada, Oiso-machi,

Naira-gun, and Reiji Sakinroto, Takaoka-sln', Japan, as-

signors to Nippon Soda Kabushiki Kaisha, Tokyo-to,

Japan, a company of Japan No Drawing. Filed June 4, 1965, Ser. No.461,541

6 Claims. (Cl. 260-453) ABSTRACT (IF THE DISCLQSURE Acaricides havinghigh activity against adults and eggs of mites, said compounds havingthe general formula 0 J11 wherein R represents methyl or ethyl and Rrepresents methyl, ethyl, propyl, allyl or CH2CECH.

The novel compounds which are provided by this invention are3,6-dichloro-2-alkoxybenzohydroxamates of the formula I 0 Cl wherein Rrepresents a lower alkyl radical, particularly CH and C H and Rrepresents methyl, ethyl, propyl, allyl or propargyl.

It is among the advantages of the invention that the compounds of theinvention have sufiicient low phytotoxicity to use Without any injury onliving plants and extremely low mammalian toxicity.

The novel compounds 3,6-dichloro-2-alkoxybenzohydroxamates may beprepared by several methods. In a convenient method the compounds areprepared through the reaction of 3,6-dichloro-2-alkoxyhenzohydroxamicacid with reagents such as dialkyl sulfate, alkyl halides, alkenylhalides and alkynyl halides. This reaction is carried out in alcoholicaqueous solution in the presence of a dehydrochlorination agent such asalkali metal hydroxide and alkali metal carbonate. In an alternativemethod, the compounds may be obtained by reacting alkyl3,6-dichloro-Z-alkoxybenzoate with O-substituted hydroxyl amines such asO-alkylhydroxylamines, O-alkenylhydroxylamines andO-alkynylhydroxylamines. This reaction is carried out in alcoholicsolution in the presence of an equimolecular quantity of alkali metalalkoxide. In a further alternative method, the compounds may also beprepared by reacting 3,6-dichloro-2-alkoxybenzoyl chloride withO-substituted hydroxylamines such as O-alkylhydroxylamines, oalkenylhydroxylamines and O-alkynylhydroxylamines. This reaction iscarried out in an organic solvent in the presence of adehydrochlorination agent such as tertiary amines and alkali metalcarbonate.

3,352,899 Patented Nov. 14, 1967 The following examples, which morefully describe the invention, are illustrations, but not a limitationthereof.

Example I Cl OOH;

l Cl

A solution of 21.4 g. of 3,6-dichloro-2-methoxybenzoyl chloride in 100ml. of chloroform was added dropwise with vigorous stirring into amixture consisting of 9.4 g. of O-methylhydroxylamine hydrochloride,33.1 g. of potassium carbonate, 150 ml. of water and ml. of chloroform.The mixture was stirred at room temperature for further 5 hours, afterwhich the layers were separated. The chloroform layer was washed with 50ml. of diluted hydrochloric acid aqueous solution, and washed with 50ml. of saturated aqueous solution of sodium bicarbonate after waterwashing, and then washed with more water. The washed chloroform solutionwas dried over magnesium sulfate, and then concentrated in vacuo. Theresidue gave 13.4 g. of the desired compound as white crystals, M.P.117-118 C., when recrystallized from benzene.

Example II About 40 ml. of an aqueous solution of 2.9 g. of potassiumhydroxide and 0.5 g. of sodium carbonate was added to a cooled solutionof 11.8 g. of 2,6-dichloro- 2-methoxybenzohydroxaniic acid and 7.8 g. ofdiethyl sulfate in ml. of methanol at a temperature of 15- 17 C., withvigorous stirring, over a period of 5 minutes. The reaction mixture wasstirred for additional 7 hours at a temperature of 20-30 C. Theresulting mixture was concentrated in vacuo, and the residue wasacidified with 1 ml. of conc-HCl and extracted with ml. of chloro .form.The chloroform layer was washed with 50 ml. of

saturated aqueous solution of sodium bicarbonate, washed with water, anddried over magnesium sulfate. The dried chloroform solution wasconcentrated in vacuo. The residue gave 12 g. of the desired compound aswhite 1 crystals, M.P. 123.0-1245 C., after recrystallization frombenzene.

Example III or 0on3 CNH O-CHB OH=CHB To a cooled solution of 11.8 g. of3,6-dichloro- Z-methoxybenzohydroxamic acid and 6.7 g. of allyl bromidein 80 ml. of methanol was added 40 ml. of an aqueous solution containing2.9 g. of potassium hydroxide and 0.5 g. of sodium carbonate at atemperature of 19- 27 C., with vigorous stirring, over a period of 10minutes.

TABLE I LEO. of Chemical Formula. Appearance M.P. C.)

0111- pound Cl 0 Ha I NHO-CH; White needles- 117-118 C1 (l) C H:

II ("1NHOC H2. CH: White needles.- 123-124.

III (|f NHOCH2. CH1.C H; White needles- 102-103 C1 1) C H;

IV $l1NH-OCH -C H=C-Hg White needles. 93. 5-94. 5

Cl (1) CH3 V GNH-O-OH:C 2 CH White needlea. 117-118 G1 (I) C H5 VI(|fNHO-C Hz-C H=C H: White needles 121-122 The acaricidal compositionsmade on the basis of the E l 1 present invention include one or more ofthe aforesaid compounds and other pesticides, and are formulated inemulsifiable concentrates, dusts, wettable powders and aerosols.

Example IV The following composition is formulated as an emulsifiableconcentrate by dissolving the active ingredient in a solvent togetherwith a surface-active agent.

Parts Compound I 2O Alkylarylpolyoxyethylene 5 Xylene 75 Thiscomposition is diluted with Water 'to give an aqueous emulsion suitablefor use in accordance with the invention.

Example V Parts Compound II Higher alcohol sulfonate 5 Diatomaceousearth 75 This composition is diluted with water to give an aqueousdispersion suitable for use in accordance with the invention.

The following dust formulationcan be prepared by blending of the activeingredients and inert diluent and then grinding the mixture to ahomogeneous powder.

Parts. Compound III 2.5 1,1-bis(4-chlorophenyl)ethanol 2.5 Alkyl arylpolyoxyethylene 0.1 Talc 94.9

This composition is applied as a dust suitable for use in accordancewith the invention.

Example VII aqueous suspensions of wettable powders formulated inaccordance with Example V were sprayed respectively;

Mortalities were counted after three, days.

Activity to eggs.Mandarin orange leaves, on which eggs of citrus redmite (Panonychus citri) were laid, were put into petri dishes. Then, thewater suspensions were sprayed according to the above test method.Ovicidal activities were observed after eight days.

TABLE H 3. A compound of the formula 01 OCHa Aizaricidal A t 1 ctivitycu eora No.0l Dosage, Mortality Phytotoxicity toxicity fi NH O CHZCHCompound Percent (Percent) against formice, 5 0

Kidney bean LD50 C1 -I e) Adult Egg 4. A compound of the formula I 0.025100 E 0.025 100 H l 0g06 100 Q fi NH O OHZOH? CH3 0. 25 100 In 0. 00s 97C1 0 Iv 0.025 100 8 89? $8 5. A compound of the formula V 0:050 96 C1OCHK Untreated 6 I C-NIIOCHz-OH=CH2 What We claim is: I I;

1. A compound having the general formula 01 R 2O 6. A compound of theformula Cl OCH;

wherein R represents methyl or ethyl and R represents 25 methyl, ethyl,propyl, allyl, or -CH2CECI'I- 2. A compound of the formula ReferencesCited 01 00113 UNITED sTATEs PATENTS 30 3,190,800 6/1965 Furst 260453 XRTfiTNLPOTCm 3,236,871 2/1966 Hinman et al. 260-453 0 C1 JOSEPH P. BRUST,Primary Examiner.

1. A COMPOUND HAVING THE GENERAL FORMULA